EP2578622A2 - Verbesserte quellbare Ölfeld-Elastomere und Herstellungs- und Verwendungsverfahren dafür - Google Patents

Verbesserte quellbare Ölfeld-Elastomere und Herstellungs- und Verwendungsverfahren dafür Download PDF

Info

Publication number
EP2578622A2
EP2578622A2 EP12187420.0A EP12187420A EP2578622A2 EP 2578622 A2 EP2578622 A2 EP 2578622A2 EP 12187420 A EP12187420 A EP 12187420A EP 2578622 A2 EP2578622 A2 EP 2578622A2
Authority
EP
European Patent Office
Prior art keywords
metal
oilfield
valves
elastomers
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP12187420.0A
Other languages
English (en)
French (fr)
Other versions
EP2578622A3 (de
Inventor
Byong Jun Kim
Keith Charles Spacey
William David Breach
Deborah Lynn Banta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Weatherford Technology Holdings LLC
Original Assignee
Weatherford Lamb Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Weatherford Lamb Inc filed Critical Weatherford Lamb Inc
Publication of EP2578622A2 publication Critical patent/EP2578622A2/de
Publication of EP2578622A3 publication Critical patent/EP2578622A3/de
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/243—Two or more independent types of crosslinking for one or more polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/08—Homopolymers or copolymers of acrylic acid esters

Definitions

  • Embodiments of the present invention relate to new swellable elastomeric compositions comprising a crosslinkable elastomer or a mixture of crosslinkable elastomers, a cure system, a co-cure system and optional ionic additive system, where the elastomeric composition is aqueous swellable and forms a network including covalent and ionic crosslinks.
  • embodiments of the present invention relate to new swellable elastomeric compositions comprising a crosslinkable elastomer or a mixture of crosslinkable elastomers, a cure system, a co-cure system and optional ionic additive system, where the elastomeric composition is aqueous swellable and forms a network including covalent and ionic crosslinks.
  • the compositions are well suited for oilfield applications and other applications using swellable polymeric compositions.
  • the compositions also show improved swelling and physical properties.
  • United States Pat. No. 7,373,991 is aware of problems with current swellable elastomeric composition including high amounts of polymeric swelling agent, so called superabsorbent polymer (SAP).
  • SAP superabsorbent polymer
  • United States Pat. No. 7,373,991 tries to reduce the use of SAPs in the water-swellable elastomer formulations by reacting a linear or branched polymer having residual ethylenic unsaturation with an ethylenically unsaturated organic monomer having at least one reactive moiety selected from the group consisting of acid, acid anhydride, and acid salt.
  • Embodiments of the present invention provide water swellable elastomeric compositions for use in oilfield applications, where the compositions include a crosslinkable elastomer or a mixture of elastomers, a covalent crosslinking system, an ionic crosslinking system and optionally an ionic additive system, where the ionic crosslinking system and the optional ionic additive system produce ionic domains in the resulting networks, the elastomeric compositions are aqueous swellable and networks include covalent and ionic crosslinks.
  • the term "network" means a composition including molecular chains held together by crosslinks between the molecular chains.
  • Embodiments of the present invention provide water swellable elastomeric compositions for use in oilfield applications, where the compositions include a crosslinkable elastomer or a mixture of elastomers, a primary crosslinking system, a secondary crosslinking system and optionally an ionic additive system, where the secondary crosslinking system and the optional ionic additive system produce ionic domains in the resulting networks, the elastomeric compositions are aqueous swellable and networks include covalent and ionic crosslinks.
  • Embodiments of the present invention provide water swellable elastomeric compositions for use in oilfield applications, where the compositions include a crosslinkable elastomer or a mixture of elastomers, a crosslinking system, a co-crosslinking system and optionally an ionic additive system, where the co-crosslinking system and the optional ionic additive system produce ionic domains in the resulting networks, the elastomeric compositions are aqueous swellable and networks include covalent and ionic crosslinks.
  • the co-crosslinking system includes metal-containing poly-functional organic compounds and the optional ionic additive system includes metal-containing mono-functional organic compounds.
  • the co-crosslinking system includes metal-containing di-functional organic compounds and metal-containing tri-functional organic compounds and the optional ionic additive system includes metal-containing mono-functional organic compounds. In other embodiments, the co-crosslinking system includes metal-containing di-functional organic compounds and the optional ionic additive system includes metal-containing mono-functional organic compounds.
  • Embodiments of the present invention provide water swellable elastomeric compositions for use in oilfield applications, where the compositions include a crosslinkable elastomer or mixture or elastomers, a cure system, a co-cure system and optionally an ionic additive system, where the co-cure system and the optional ionic additive system produce ionic domains in the resulting networks, the elastomeric compositions are aqueous swellable and networks include covalent and ionic crosslinks.
  • the co-cure system includes metal-containing poly-functional organic compounds and the optional ionic additive system includes metal-containing mono-functional organic compounds.
  • the co-cure system includes metal-containing di-functional organic compounds and metal-containing tri-functional organic compounds and the optional ionic additive system includes metal-containing mono-functional organic compounds, In other embodiments, the co-cure system includes metal-containing di-functional organic compounds and the optional ionic additive system includes metal-containing mono-functional organic compounds.
  • An oilfield apparatus comprising a high temperature swellable elastomeric composition comprising an elastomer or a mixture of elastomers, a cure system, a co-cure system and optional ionic additive system, where the co-cure system and the optional ionic additive system produce ionic domains in the resulting networks, the elastomeric compositions are aqueous swellable and networks include covalent and ionic crosslinks. Due to the structures of the polymeric networks of the compositions of this invention, the compositions show improved rate of swelling in water, brines and aqueous solutions, swellability, and/or physical properties of the compositions.
  • An oilfield assembly for exploring for, drilling for, testing for, or producing hydrocarbons comprising: (a) one or more oilfield apparatus selected from the group consisting of tubing, jointed pipe, sucker rods, electric submersible pumps, submersible pump motor protector bags, packers, packer elements, blow out preventers, blow out preventer elements, self-healing cements, proppants, O-rings, T-rings, centralizers, hangers, plugs, plug catchers, check valves, universal valves, spotting valves, differential valves, circulation valves, equalizing valves, safety valves, fluid flow control valves, sliding seals, connectors, disconnect tools, downhole filters, motor heads, retrieval and fishing tools, bottom hole assemblies, seal assemblies, snap latch assemblies, anchor latch assemblies, shear-type anchor latch assemblies, no-go locators, sensor protectors, gaskets, pump shaft seals, tube seals, valve seals, seals and insulators used in electrical components, seals used in fiber optic connections, pressure sealing elements for fluids,
  • a method comprising (a) selecting one or more oilfield apparatus having a component comprising an elastomeric composition comprising an elastomer or a mixture of elastomers, a cure system, a co-cure system and optional ionic additive system, where the co-cure system and the optional ionic additive system produce ionic domains in the resulting networks, the elastomeric compositions are aqueous swellable and networks include covalent and ionic crosslinks; and (b) using the one or more oilfield apparatus in an oilfield operation, thus exposing the oilfield apparatus to an oilfield environment.
  • the oilfield apparatus is selected from the group consisting of submersible pump motor protector bags, packer elements, blow out preventer elements, self-healing cements, proppants, O-rings, T-rings, centralizers, hangers, plugs, plug catchers, check valves, universal valves, spotting valves, differential valves, circulation valves, equalizing valves, safety valves, fluid flow control valves, sliding seals, connectors, disconnect tools, downhole filters, motor heads, retrieval and fishing tools, bottom hole assemblies, seal assemblies, snap latch assemblies, anchor latch assemblies, shear-type anchor latch assemblies, no-go locators, sensor protectors, gaskets, pump shaft seals, tube seals, valve seals, seals and insulators used in electrical components, seals used in fiber optic connections, pressure sealing elements for fluids, and combinations thereof.
  • Figure 1 depicts an embodiment of an elastomeric polymer network composition including ionic bonds.
  • Figure 2 depicts two super absorbent polymeric (SAP) agents: sodium polyacrylate and poly(acryl amide-co-acrylic acid) potassium salt.
  • SAP super absorbent polymeric
  • Figure 3 depicts an embodiment of an elastomeric polymer network composition including SAPs distributed in the network.
  • Figure 4 depicts aged swelling data for comparative example Formula A and Formulas H and I of this invention in 3 wt.% NaCl brine solution.
  • Figure 5 depicts aged swelling data for comparative example Formula A and Formulas H and I of this invention in 3 wt.% CaCl 2 brine solution.
  • compositions of this invention to produce networks having improved swellability in water, brines or other aqueous solutions, the networks have improved rates of swelling compared to composition excluding the ionic crosslinking system and the networks have improved physical properties.
  • Embodiments of this invention relate to swellable elastomeric network compositions comprising a covalent crosslinked network, an ionic crosslinked network, optionally ionic pendant groups and optionally super absorbent polymers (SAPs), where the covalent crosslinked network and the ionic crosslinked network provide the compositions with improved physical properties such as tensile stress, elongation, modulus, compression set, tear strength, and to withstand a high differential pressure in harsh downhole environments, while the ionic crosslinks, the optional ionic pendant groups and the optional SAPs provide domains for water swellability without imparting significant stress into the compositions permitting a faster rate of water osmosis into the compositions and swelling of the compositions.
  • SAPs super absorbent polymers
  • Embodiments of this invention relate to swellable elastomeric network compositions comprising a crosslinked network and interpenetrating ionic domains to form a low stress/strain swellable composition, where the crosslinks comprise covalent and ionic crosslink and the ionic domains comprise the ionic crosslinks, optional ionic pendant groups and optional super absorbent polymers (SAPs), where the crosslinked network provides the compositions with improved physical properties such as tensile stress, elongation, modulus, compression set, tear strength, and to withstand a high differential pressure in harsh downhole environments, while the ionic domains permit improved water swellability without imparting significant stress/strain into the compositions and permit a faster rate of water osmosis into the compositions and swelling of the compositions.
  • SAPs super absorbent polymers
  • the relative amount of covalent and ionic crosslinking may be varied.
  • the relative ratio of covalent crosslinks to ionic crosslinks, the crosslink densities and distributions of the covalent crosslinks to ionic crosslinks and the overall crosslink density and distribution may be varied. Such variations permit compositions to be prepared that are optimized for different conditions and environments.
  • a highly crosslinked water-swellable elastomer cannot highly and/or rapidly swell in contact with water or water-based solution.
  • the highly crosslinked molecular networks keep Super-absorbent Polymer (SAP) and base-elastomer from highly straining, which results from swelling. Therefore, it is a common practice for rubber chemists to design intentionally the swellable elastomers with a low state of cure and/or a large loading of SAP in order to achieve a high swell capability in contact with water or an aqueous solution.
  • the low state of cure and high loading of SAPs lead to poor physical and mechanical properties of the swellable elastomers or network.
  • SAP-containing elastomer swells in contact with water-based solutions. Most SAPs have the ability to absorb 200-500 times their weight in pure water. SAPs are prepared using various polymers and certain metal compounds, such as sodium and potassium salts. The driving force of water-swelling is osmotic pressure, which is caused by a chemical potential difference between the SAP and the aqueous solution. Therefore, SAPs ability to absorb water is dependent upon the ionic concentration of the aqueous solution.
  • swellable packers are mostly deployed in brine environments or other aqueous environments, rather than in pure water.
  • Such ionic aqueous solutions dramatically reduces the swell capability or swellability or rate of swelling of swellable elastomers or swellable elastomeric networks or matrices.
  • a historical solution to make water swellable elastomers effective in highly ion-concentrated aqueous solutions is to formulate a network having a low loading of curing agents such as peroxides, sulfur, sulfur donor etc. and high loading of SAPs.
  • Elastomers become practically useful after crosslinking, (so called curing, networking of molecular chains).
  • Our solution is to formulate water/hybrid swellable elastomers in a way to increase ionic density of the base elastomer during the curing process.
  • our invention is to incorporate metal ionic groups in the elastomer network during cure.
  • the ionic potential of swellable elastomers is not only driven by SAP, but also base-elastomer and the cured network.
  • FIG. 1 an embodiment of a network of this invention is shown with mono-functional linkages, di-functional linkages and tri-functional linkages due to metal ionic bonds.
  • These networks form when metal-containing organic compounds or non-organic (Si BN, Ge or other non-organic) compounds are used as a co-curing agent with traditional cure systems such as a peroxide, sulfur or sulfur donor cure systems.
  • Such co-curing agents may be used alone and/or in combination.
  • Metal-containing organic compounds, which may be used in the present invention are set forth herein.
  • network compositions of this invention may be prepared with using zinc based co-curing agents such as zinc diacrylate (ZDA) and zinc dimethacrylate (ZMA),
  • Such ionic crosslinks in the network composition of this invention increase an ionic density of swellable elastomers.
  • These composition may also include super absorbent polymers (SAPs).
  • SAPs super absorbent polymers
  • Widely used SAPs are sodium polyacrylate and poly(acryl amide-co-acrylic acid) potassium salt, which are shown in Figure 2 .
  • SAPs are higher than the H + potentials of water or aqueous solutions so that osmotic pressure is created. As a result, water migrates into the swellable elastomeric compositions until it reaches potential equilibrium.
  • SAPs are independent from base-polymer network, i.e. not chemically attached as shown in Figure 3 . It is just physically blended.
  • elastomeric compositions including between about 1 phr (parts per hundred parts of rubber or resin) and about 50 phr of a metal-containing organic co-cure agent or mixture or co-cure agents, where the co-cure agents cross-link the elastomer or rubber molecules ionically - ionic bonds.
  • the present composition are a hybrid cured elastomer network system including covalent and ionic bonds, where the ionic bonds for ionic domains within the elastomeric network improve the swell capability of the elastomers.
  • the ionic domains due to the ionic co-curing agents significantly enhance a rate of swelling, the swellability and improve the physical properties of the networks.
  • the elastomeric compositions include between about 1 phr and about 40 phr of a metal-containing organic co-cure agent or mixture or co-cure agents.
  • the elastomeric compositions include between about 1 phr and about 30 phr of a metal-containing organic co-cure agent or mixture or co-cure agents. In certain embodiments, the elastomeric compositions include between about 1 phr and about 20 phr of a metal-containing organic co-cure agent or mixture or co-cure agents. In certain embodiments, the elastomeric compositions include between about 3 phr and about 20 phr of a metal-containing organic co-cure agent or mixture or co-cure agents.
  • the elastomeric compositions including between about 3 phr and about 10 phr of a metal-containing organic co-cure agent or mixture or co-cure agents increase water swell capability, doubling it compared to swellable elastomer without metal-containing organic co-cure co-agent.
  • the present composition may thus be formulated to reduce and even minimize the loading amount of SAPs in the swellable compositions of this invention.
  • SAPs have negative impact on mechanical/physical properties of the rubber or elastomeric composition.
  • compositions including metal-containing organic co-cure agents allow for an increase in covalent crosslink density, which results in enhanced physical and mechanical properties of the final composition.
  • the co-curing agents of this invention the inventors do not have to offset physical and mechanical properties of swellable elastomeric compositions to enhance water swell capability.
  • composition embodying this invention may comprise:
  • composition embodying this invention may comprise:
  • composition embodying this invention may comprise:
  • composition embodying this invention may comprise:
  • Suitable water swellable elastomers for use in an embodiment of the present invention include without limitation, water/aqueous swellable elastomers and water/oil hybrid swellable elastomers and mixtures and/or combination thereof - mixtures mean that the network is composed of a mixture of the elastomers, while combination mean that the net work is composed of domains of one elastomer or domains including a mixture of elastomers.
  • Suitable metal-containing compound include, without limitation, metal acrylates, metal methacrylates, metal acetates, metal carboxylates, metal sulfonates, metal sulfates, metal phosphites, metal phosphates, metal silicon analogs, metal germanium analogs, metal boron nitride analogs, similar organic or pseudo organic compounds, and mixture and/or combinations thereof, where the metals are selected from the group consisting of alkali metals, alkaline earth metals, transition metals, lanthanide metals, actinide metals, metalloids and mixtures and/or combinations thereof.
  • the metal-containing compounds may be mono-functional, di-functional, tri-functional, tetra-functional, penta-functianal, or higher-functional depending on the valence state of the metal.
  • Exemplary non-limiting examples of mono-functional organic compounds include:
  • di-functional organic compounds include:
  • tri-functional organic compounds include:
  • An elastomeric composition embodying this invention may comprise any number of additives, fillers, and the like, depending on the end use of the oilfield element.
  • One such additive is an inorganic swelling agent, which functions to enhance the water-swellability of the elastomeric compositions useful in an embodiment of the invention.
  • Inorganic swelling agents useful for this purpose include alkali- and alkaline earth carbonates, such as, but not limited to, carbonates of sodium (sodium carbonate; soda ash). Sodium carbonate may also act as a foaming agent and enhance the permeation and rate of swelling.
  • Apparatus in embodying the invention include those wherein the elastomeric composition is vulcanized by an organic vulcanizing agent.
  • organic vulcanization elements useful in an embodiment of the invention may be selected from organic peroxides, such as, but not limited to, dicumyl peroxide.
  • the base elastomer may include a zwitterionic polymer blended into the base elastomer, or a copolymer of zwitterionic monomers and unsaturated monomers like butadiene and isoprene, allowing production of a crosslinkable elastomer that swells in high salinity brines as well as in hydrocarbon oil-based fluids.
  • a diene monomer may be included for crosslinking cites.
  • Representative zwitterionic polymers useful in an embodiment of the invention include, but are not limited to, copolymers of 2-methacryloyloxyethyl-2'-trimethylammanium ethyl phosphate inner salt (MPC) with comonomers, including a variety of hydrophobic monomers, for instance C 4-18 -alkyl methacrylate, and fluoroalkyl methacrylates.
  • MPC 2-methacryloyloxyethyl-2'-trimethylammanium ethyl phosphate inner salt
  • the elastomer composition may be selected from any elastomer listed in ASTM D1418, and may comprise one or more non-elastomeric polymers selected from natural and synthetic polymers, including those listed in ASTM D 1600-92, "Standard Terminology for Abbreviated Terms Relating to Plastics".
  • the elastomer and non-elastomer may be layered, wherein individual layers may be the same or different in composition and thickness, interpenetrating networks, and the like.
  • the elastomer composition may include fillers, plasticizers, accelerants, fibers, nanoflakes and/or nanoplatelets.
  • Non-elastomeric polymers may include, but are not limited to, thermoplastic polymers, such as polyolefins, polyamides, polyesters, thermoplastic polyurethanes and polyurea urethanes, copolymers, and blends thereof, and the like; one or more thermoset polymers, such as phenolic resins, epoxy resins, and the like.
  • thermoplastic polymers such as polyolefins, polyamides, polyesters, thermoplastic polyurethanes and polyurea urethanes, copolymers, and blends thereof, and the like
  • thermoset polymers such as phenolic resins, epoxy resins, and the like.
  • Apparatus within the invention include those wherein the oilfield element may be any element exposed to water, brine, low and high pH fluids, and/or hydrocarbon fluids, such as, but not limited to packer elements (the elastomeric components), submersible pump motor protector bags, sensor protectors, blow out preventer elements, O-rings, T-rings, gaskets, pump shaft seals, tube seals, valve seals, seals and insulators used in electrical components, such as wire and cable semiconducting shielding and/or jacketing, power cable coverings, seals and bulkheads such as those used in fiber optic connections and other tools, and pressure sealing elements for fluids (gas, liquid, or combinations thereof).
  • packer elements the elastomeric components
  • submersible pump motor protector bags such as, but not limited to packer elements (the elastomeric components), submersible pump motor protector bags, sensor protectors, blow out preventer elements, O-rings, T-rings, gaskets, pump shaft seals, tube seals, valve
  • Another aspect embodying the invention are oilfield assemblies for exploring for, testing for, or producing hydrocarbons, one oilfield assembly comprising:
  • Yet another aspect embodying the invention are methods of exploring for, drilling for, or producing hydrocarbons, one method comprising:
  • Methods embodying the invention may include, but are not limited to, running one or more oilfield elements into a wellbore using one or more surface oilfield elements, and/or retrieving the oilfield element from the wellbore.
  • the oilfield environment during running and retrieving may be the same or different from the oilfield environment during use in the wellbore or at the surface.
  • An embodiment of the invention describes apparatus comprising an elastomeric material useful in oilfield applications, including hydrocarbon exploration, drilling, testing, completion, and production activities.
  • oilfield includes land based (surface and sub-surface) and sub-seabed applications, and in certain instances seawater applications, such as when hydrocarbon exploration, drilling, testing or production equipment is deployed through seawater.
  • oilfield includes hydrocarbon oil and gas reservoirs, and formations or portions of formations where hydrocarbon oil and gas are expected but may ultimately only contain water, brine, or some other composition.
  • a typical use of the apparatus comprising an elastomeric component will be in downhole applications, such as zonal isolation of wellbores, although the invention is not so limited.
  • a “wellbore” may be any type of well, including, but not limited to, a producing well, a non-producing well, an injection well, a fluid disposal well, an experimental well, an exploratory well, and the like.
  • Wellbores may be vertical, horizontal, deviated some angle between vertical and horizontal, and combinations thereof, for example a vertical well with a non-vertical component.
  • elastomer/hydrogel blends show a nonuniform swelling and develop blisters on the surface when exposed to water. After a few days of exposure to water these blisters burst open and hydrogel particles are ejected out of the blend leaving behind cracks in the elastomer.
  • Suitable curable elastomers include, without limitation, nitrile-butadiene rubber (NBR), hydrogenated NBR, hydrogenated nitrile rubber (HNBR), chemically functionalized NBR (Carboxylated NBR), ethylene-propylene-diene-copolymer (EPDM), ethylene-propylene ruber (EPR), fluorinated elastomers (FKM, FFKM, FEPM), styrene-butadiane rubber (SBR), hydrogenated styrene-butadiene rubber (hSBR), isoprene-butadiene rubber (IBR), hydrogenated isoprene-butadiene rubber (hIBR), styrene-isoprene rubber (SIR), hydrogenated styrene-isoprene rubber (hSIR), styrene-butadiene-isoprene (SIBR), hydrogenated styrene-butadiene-iso
  • Elastomeric compositions and methods of making same described herein provide a concept of making low-cost commercial elastomers containing some double bonds swellable in water.
  • "Elastomer” as used herein is a generic term for substances emulating natural rubber in that they stretch under tension, have a high tensile strength, retract rapidly, and substantially recover their original dimensions.
  • the term includes natural and man-made elastomers, and the elastomer may be a thermoplastic elastomer or a non-thermoplastic elastomer.
  • the term includes blends (physical mixtures) of elastomers, as well as copolymers, terpolymers, and multi-polymers.
  • Examples include ethylene-propylene-diene polymer (EPDM), various nitrile rubbers which are copolymers of butadiene and acrylonitrile such as Buna-N (also known as standard nitrile and NBR). By varying the acrylonitrile content, elastomers with improved oil/fuel swell or with improved low-temperature performance can be achieved. Specialty versions of carboxylated high-acrylonitrile butadiene copolymers (XNBR) provide improved abrasion resistance, and hydrogenated versions of these copolymers (HNBR) provide improve chemical and ozone resistance elastomers. Carboxylated HNBR is also known.
  • the phrases "swellable in water”, “water-swellable”, “water swellability” and the like are used interchangeably and mean that the elastomeric composition swells in contact with aqueous system including pure water, brines, and other aqueous solutions.
  • the compositions of this invention will generally swell at least up to 25 percent in an aqueous system. In certain embodiments, the compositions may swell at least 1000 percent.
  • the amount of swellability of a compositions depends at least on sample thickness, the elastomers used to form the composition, the ratio of covalent crosslinks to ionic crosslinks, the amount of the optional ionic additive system, and crosslink density.
  • the compositions may swell at least 200 percent of their original volume after soaking in tap water at 100°C for 24 hours.
  • the phrases "swellable in oil”, “oil-swellable”, “oil swellability” and the like are used interchangeably and mean that the elastomeric composition swells in organic systems or nonaqueous systems such as in organic solvents.
  • the compositions of this invention will swell at least 25 percent in an organic system.
  • the compositions may swell at least 100 percent in an organic system.
  • the compositions may swell at least 300 percent of their original volume after soaking in kerosene at 100°C for 24 hours.
  • Elastomeric compositions useful in an embodiment of the invention include those that are: 1) low-cost and water-swellable; 2) low-cost and water- and oil-swellable; 3) swellable in high-salinity brines like completion fluids; 4) high-temperature stable; and 5) low-cost and swellable in very low pH solutions.
  • Elastomeric compositions disclosed herein may be used for sealing applications in oilfield industry especially for applications such as swellable packers, flow control, sand control, and coil tubing slack management. These materials may also be used as self-healing seals for downhole applications.
  • elastomeric compositions disclosed herein are, at least presently, relatively low cost, commercially available materials.
  • the elastomeric compositions useful in oilfield elements embodying the invention may be readily made in small or large quantities by using standard elastomer manufacturing techniques such as Banbury and two roll mill compounding.
  • linear or branched polymer having residual ethylenic unsaturation functions as the main structural component of the elastomer, and, depending on its length, solubility parameter, and other factors, largely determines the oil-swellability of the composition and therefore the oil-swellability of the oilfield element.
  • linear or branched chain polymers having residual ethylenic unsaturation include polymers of ethylene-propylene-diene monomer (EPDM).
  • Other examples of linear or branched chain polymers having residual ethylenic unsaturation include natural rubber, polybutadiene, polyisoprene, ethylene-octene-based rubber and the like. Both cis and trans versions, as well as derivatized versions (side chains) of any of these may be used, as long as they do not affect the basic swellability properties sought in the final product elastomeric composition.
  • Ethylene-propylene-diene monomer polymers may comprise an ethylene copolymer or terpolymer of a (C 3 -C 10 )diene-olefin and a non-conjugated diene or triene, and may have an average molecular weight ranging from about 1000 to 40,000, or from 6,000 to 10,000, on which, at some stage of one of the processes, has been grafted or added physically 0.1 to 10 percent by weight, or 1.0 to 3.0 percent by weight of an ethylenically unsaturated carboxylic function.
  • More complex polymer substrates may be prepared using a third component.
  • the third component if used, may be a polyene monomer selected from non-conjugated dienes and trienes.
  • the non-conjugated diene component may have from 5 to 14 carbon atoms in the chain.
  • the diene monomer is characterized by the presence of a vinyl group in its structure and can include cyclic and bi-cyclo compounds.
  • a mixture of more than one diene, more than one triene, or mixture of dienes and trienes may be used.
  • Representative dienes include, but are not limited to, non-conjugated dienes such as dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbomene 1,4-hexadiene, 1,4-cyclohexadiene, 1,5-heptadiene, and 1,6-octadiene.
  • non-conjugated dienes such as dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbomene 1,4-hexadiene, 1,4-cyclohexadiene, 1,5-heptadiene, and 1,6-octadiene.
  • the triene component if used, will have at least two non-conjugated double bonds, and may have up to about 30 carbon atoms in the chain.
  • Typical trienes useful in preparing elastomers useful in an embodiment of the invention include, but are not limited to, 1-isopropylidene-3a,4,7,7a-tetrahydroindene, 1-isopropylidenedicyclopentadiene, dehydroisodicyclopenta-diene, and 2-(2-methylene-4-methyl-3-pentenyl)-2.2.1-bicyclo-5-heptene.
  • the elastomeric composition may comprise any number of additives, fillers, and the like, depending on the end use of the oilfield element. It is believed that these materials may be added to alter or modify certain properties, when added in amounts up to about 5 parts per hundred weight of composition.
  • Suitable cure systems include, without limitation, sulfur based cure systems, peroxide based cure systems, radiation based cure systems, or mixtures and combinations thereof.
  • Exemplary crosslinking system include, without limitation, peroxides, sulfur, sulfur-donors, amines, phenolic resins, metal oxides, irradiation sources, bisphenol, any other crosslinking system that can generate free radicals, ions, or any other reactive sites on the molecular chain of elastomers, or mixtures and combinations thereof.
  • Apparatus in accordance with the invention include those wherein the elastomeric composition is vulcanized by an organic vulcanizing agent.
  • An inorganic vulcanization agent may be included, such as one or more inorganic metallic oxides, and certain metals such as selenium. Heat, high energy radiation, chemical accelerators and other means may be used in conjunction with the organic vulcanization agent.
  • organic vulcanization elements useful in an embodiment of the invention may be selected from organic peroxides, such as dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl-peroxide, di(tert-butylperoxyisopropyl)benzene, dibenzoyl peroxide, di(2,4-dichlorobenzoyl)peroxide, di(4-methylbenzoyl)peroxide, 2,5-Dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne, butyl 4,4-di(tert-butylperoxy)valerate, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-but
  • Halogenated quinones may be used as organic vulcanization elements, including those such as chlorinated quinones such as chloranil and 2,3-dichloro-5,6-dicyanoquinone, and the like, and mixtures thereof.
  • Nitrobenzenes, nitrotoluenes, nitroxylenes, and ortho-, meta-, and para-derivatives thereof may be used as organic vulcanization elements.
  • Useful p-nitrobenzene derivatives include, but are not limited to, for example, p-nitrofluorobenzene, p-nitrochlorobenzene, p-nitrobromobenzene, p-nitroiodobenzene, p-nitrophenol, p-nitrobenzoic acid, and p-nitrobenzoic acid chloride.
  • nitrobenzene derivatives include 2-methyl-4-nitrophenol, 2-trifluoromethyl-4-nitrophenal, 2-methyl-4-nitrobenzoic acid, 2-methyl-4-nitrobenzoic acid chloride, 2-trifluoromethyl-4-nitrobenzoic acid, 2-trifluoromethyl-4-nitrobenzoic acid chloride or acetanilide.
  • a combination thereof may be suitably selected depending upon the particular purpose taking into consideration the reactivity and the availability of the materials. It should be mentioned that those exemplified here are only examples.
  • fillers may reduce the swelling and permeability of polymeric materials. In general, the reduction in swelling and permeability increases as the filler concentration is increased.
  • the permeability of polymeric materials may also depend on the shape and aspect ratio of the filler particles. Platelet like fillers such as nanoclays, preferably with small thickness ( ⁇ 0.1 micrometer) and length less than 200 micrometers, when aligned, may create a torturous path for diffusing fluid molecules and therefore may enhance the barrier properties of the resultant materials compared with barrier properties of raw polymer of the same composition and morphology.
  • Suitable additives for use in the compositions of this invention include fillers and reinforcing fillers such as carbon black, silica, clay, etc., process aids, antioxidants, antiozonants, flame retardants, etc. or mixtures or combinations thereof.
  • Relatively non-elastic polymeric materials such as thermoplastic and thermoset polymeric materials, may be combined or mixed with the elastomers, at a weight of from about 1 to 40 phr of the elastomer composition.
  • Relatively non-elastic polymeric materials useful in an embodiment of the invention may be selected from natural and synthetic polymers, blends of natural and synthetic polymers, and layered versions of polymers, wherein individual layers may be the same or different in composition and thickness.
  • the non-elastic polymer may comprise one or more thermoplastic polymers and/or one or more thermoset and/or thermally cured polymers, and combinations thereof.
  • thermoplastic material is defined as a polymeric material (preferably, an organic polymeric material) that softens and melts when exposed to elevated temperatures and generally returns to its original condition, i.e., its original physical state, when cooled to ambient temperatures.
  • the thermoplastic material may be heated above its softening temperature, and preferably above its melting temperature, to cause it to flow and form the desired shape of the oilfield element in conjunction with the elastomer. After the desired shape is formed, the thermoplastic substrate is cooled and solidified. In this way, thermoplastic materials (including thermoplastic elastomers) can be molded into various shapes and sizes.
  • Moldable thermoplastic materials that may be used are those having a high melting temperature, good heat resistant properties, and good toughness properties such that the oilfield element or assemblies containing these materials operably withstand oilfield conditions without substantially deforming or disintegrating.
  • Thermoplastic polymers useful as polymeric matrix materials are those able to withstand expected temperatures, temperature changes, and temperature differentials (for example a temperature differential from one surface of a gasket to the other surface material to the other surface) during use, as well as expected pressures, pressure changes, and pressure differentials during use, with a safety margin on temperature and pressure appropriate for each application.
  • thermoplastic materials suitable for use in an embodiment of the invention in oilfield elements according to the present invention include polyolefins, polyamides, polyesters, thermoplastic polyurethanes and polyurea urethanes, PP, PE, PP-PE copolymer, PVC and other polyolefins, polyamides, polyetheretherketones (PEEK), polyaryletherketones (PAEK), polyetherimides (PEL), copolymers oftetrafluoroethylene and perfluorovinylether (PFA), perfluoroalkoxy copolymers (MFA), polycarbonates, polyetherimides, polyesters, polysulfones, polystyrenes, acrylonitrile-butadiene-styrene block copolymers, acetal polymers, polyaxnides, copolymers, blends, and other combinations thereof, and the like.
  • polyamides and polyesters may provide better performance.
  • Polyamide materials are useful at least because they are inherently tough and heat resistant, and are relatively inexpensive.
  • Polyamide resin materials may be characterized by having an amide group, i.e., --C(O)NH--.
  • Various types of polyamide resin materials i.e., nylons, can be used, such as nylon 6/6 or nylon 6.
  • nylon 6 may be used if a phenolic-based coating is used because of the excellent adhesion between nylon 6 and phenolic-based coatings.
  • Nylon 6/6 is a condensation product of adipic acid and hexamethylenediamine.
  • Nylon 6/6 has a melting point of about 264°C.
  • Nylon 6 is a polymer of ⁇ -caprolactam. Nylon 6 has a melting point of about 223°C. and a tensile strength of about 700 kg/cm 2 .
  • Examples of commercially available nylon resins useable in oilfield elements according to the present invention include those known under the trade designations VYDYNE from Solutia, St.
  • thermoset (thermally cured) polymers for use in elastomeric compositions of the invention include phenolic resins, epoxy resins, phenoxy, phenolic, ester, polyurethane, polyurea, and the like.
  • Thermoset molding compositions known in the art are generally thermosetting resins containing inorganic fillers and/or fibers. Upon heating, thermoset monomers initially exhibit viscosities low enough to allow for melt processing and molding of an article from the filled monomer composition. Upon further heating, the thermosetting monomers react and cure to form hard resins with high stiffness.
  • the elastomeric composition may comprise other ingredients in addition to the monomers, polymers, and other ingredients already mentioned, such as fillers, coupling agents, suspension agents, pigments, and the like.
  • the elastomer composition may include an effective amount of a fibrous reinforcing material.
  • an "effective amount" of a fibrous reinforcing material is a sufficient amount to impart at least improvement in the physical characteristics of the oilfield element, i.e., heat resistance, toughness, flexibility, stiffness, shape control, adhesion, etc., but not so much fibrous reinforcing material as to give rise to any significant number of voids and detrimentally affect the structural integrity of the oilfield element.
  • the amount of the fibrous reinforcing material in the elastomeric composition may be any amount that does not substantially detrimentally affect the desired swellability properties achieved by the elastomeric composition, and may be within a range of about 1-40 parts, or within a range of about 5-35 parts, or within a range of about 15-30 parts by weight, for every 100 parts by weight of polymer.
  • the fibrous reinforcing material may be in the form of individual fibers or fibrous strands, or in the form of a fiber mat or web.
  • the mat or web can be either in a woven or nonwoven matrix form.
  • useful reinforcing fibers in applications of the present invention include metallic fibers or nonmetallic fibers.
  • the nonmetallic fibers include glass fibers, carbon fibers, mineral fibers, synthetic or natural fibers formed of heat resistant organic materials, or fibers made from ceramic materials.
  • heat resistant organic fibers it is meant that useable organic fibers must be resistant to melting, or otherwise breaking down, under the conditions of manufacture and use of the oilfield elements of the present invention.
  • useful natural organic fibers include wool, silk, cotton, or cellulose.
  • useful synthetic organic fibers include polyvinyl alcohol fibers, polyester fibers, rayon fibers, polyamide fibers, acrylic fibers, aramid fibers, or phenolic fibers.
  • any ceramic fiber is useful in applications of the present invention.
  • An example of a ceramic fiber suitable for the present invention is NEXTEL which is commercially available from 3M Co., St. Paul, Minn. Glass fibers may be used, at least because they impart desirable characteristics to the oilfield elements and are relatively inexpensive.
  • suitable interfacial binding agents exist to enhance adhesion of glass fibers to thermoplastic materials.
  • Glass fibers are typically classified using a letter grade. For example, E glass (for electrical) and S glass (for strength). Letter codes also designate diameter ranges, for example, size "D” represents a filament of diameter of about 6 micrometers and size "G” represents a filament of diameter of about 10 micrometers.
  • Useful grades of glass fibers include both E glass and S glass of filament designations D through U.
  • Preferred grades of glass fibers include E glass of filament designation "G” and S glass of filament designation "G.”
  • Commercially available glass fibers are available from Specialty Glass Inc., Oldsmar, Fla.; Johns Manville, Littleton, Colorado; and Mo-Sci Corporation, Rolla, Mo.
  • the glass fibers may be accompanied by an interfacial binding agent, i.e., a coupling agent, such as a silane coupling agent, to improve the adhesion to the thermoplastic material.
  • a coupling agent such as a silane coupling agent
  • silane coupling agents include "Z-6020” and "-6040,” available from Dow Coming Corp., Midland, Mich.
  • the elastomer compositions of the present invention may further include an effective amount of a toughening agent.
  • a toughening agent is to increase the impact strength of the oilfield elements.
  • an effective amount of a toughening agent it is meant that the toughening agent is present in an amount to impart at least improvement in toughness without the component becoming too flexible.
  • Elastomeric portions of oilfield elements of the present invention may contain between about 1 and 30phr of a toughening agent. For example, the less elastomeric characteristics a toughening agent possesses, the larger quantity of the toughening agent may be required to impart desirable properties to the oilfield elements of the present invention.
  • Toughening agents that impart desirable stiffness characteristics to the oilfield elements of the present invention include rubber-type polymers and plasticizers.
  • the rubber toughening agents may be mentioned, and synthetic elastomers.
  • preferred toughening agents include: toluenesulfonamide derivatives (such as a mixture ofN-butyl- and N-ethyl-p-toluenesulfonamide, commercially available from Akzo Chemicals, Chicago, III., under the trade designation KETJENFLEX 8; styrene butadiene copolymers; polyether backbone polyamides (commercially available from Atochem, Glen Rock, N.J., under the trade designation PEBAX); rubber-polyamide copolymers (commercially available from DuPont, Wilmington, Del., under the trade designation ZYTEL FN); and functionalized triblock polymers of styrene-(ethylene butylene)-st
  • ULTRAMID B3ZG6 is a nylon resin containing a toughening agent and glass fibers that is useful in the present invention.
  • inorganic fillers are also known as mineral fillers.
  • a filler is defined as a particulate material, typically having a particle size less than about 100 micrometers, preferably less than about 50 micrometers, but larger than about 1 micrometer.
  • useful fillers for applications of the present invention include carbon black, calcium carbonate, silica, calcium metasilicate, cryolite, phenolic fillers, or polyvinyl alcohol fillers. If a filler is used, it is theorized that the filler may fill in between reinforcing fibers if used, and may prevent crack propagation through the elastomer. Typically, a filler would not be used in an amount greater than about 20 percent based on the weight of the elastomeric composition.
  • An apparatus embodying the invention in particular the elastomeric elements, if filled with fillers, may also contain coupling agents.
  • a coupling agent may be desired.
  • Coupling agents may operate through two different reactive functionalities: an organofunctional moiety and an inorganic functional moiety.
  • an organofunctional moiety When a resin/filler mixture is modified with a coupling agent, the organofunctional group of the coupling agent becomes bonded to or otherwise attracted to or associated with the uncured resin.
  • the inorganic functional moiety appears to generate a similar association with the dispersed inorganic filler.
  • the coupling agent acts as a bridge between the organic resin and the inorganic filler at the resin/filler interface. In various systems this results in:
  • coupling agent includes mixtures of coupling agents.
  • An example of a coupling agent that may be found suitable for this invention is gamma-methacryloxypropyltrimethoxy silane known under the trade designation SILQUEST A 174 from GE Silicones, Wilton, Conn.
  • Other suitable coupling agents are zircoaluminates, and titanates.
  • the elastomeric composition may include a shape stabilizer, i.e., a thermoplastic polymer with a melting point higher than that described above for the thermoplastic material.
  • Suitable shape stabilizers include, but are not limited to, poly(phenylene sulfide), polyimides, and polyaramids.
  • An example of a preferred shape stabilizer is polyphenylene oxide nylon blend commercially available from GE Plastics, Pittsfield, Mass., under the trade designation GTX 910.
  • oilfield assembly is the complete set or suite of oilfield elements that may be used in a particular job. All oilfield elements in an oilfield assembly may or may not be interconnected, and some may be interchangeable.
  • An "oilfield element” includes, but is not limited to one or more items or assemblies selected from zonal isolation tool elastomeric elements, packer elements, blow out preventer elements, self-healing cements, proppants, O-rings, T-rings, electric submersible pump protectors, centralizers, hangers, plugs, plug catchers, check valves, universal valves, spotting valves, differential valves, circulation valves, equalizing valves, safety valves, fluid flow control valves, connectors, disconnect tools, downhole filters, motor heads, retrieval and fishing tools, bottom hole assemblies, seal assemblies, snap latch assemblies, anchor latch assemblies, shear-type anchor latch assemblies, no-go locators, and the like.
  • a "packer” is a device that can be run into a wellbore with a smaller initial outside diameter that then expands externally to seal the wellbore.
  • Packers employ flexible, elastomeric seal elements that expand.
  • the two most common forms are the production or test packer and the inflatable packer.
  • the expansion of the former may be accomplished by squeezing the elastomeric elements (somewhat doughnut shaped) between two plates or between two conical frusta pointed inward, forcing the elastomeric elements' sides to bulge outward.
  • the expansion of the latter may be accomplished by pumping a fluid into a bladder, in much the same fashion as a balloon, but having more robust construction.
  • Production or test packers may be set in cased holes and inflatable packers may be used in open or cased holes. They may be run down into the well on wireline, pipe or coiled tubing. Some packers are designed to be removable, while others are permanent. Permanent packers are constructed of materials that are easy to drill or mill out.
  • a packer may be used during completion to isolate the annulus from the production conduit, enabling controlled production, injection or treatment.
  • a typical packer assembly incorporates a means of securing the packer against the casing or liner wall, such as a slip arrangement, and a means of creating a reliable hydraulic seal to isolate the annulus, typically by means of an expandable elastomeric element.
  • Packers are classified by application, setting method and possible retrievability.
  • Inflatable packers are capable of relatively large expansion ratios, an important factor in through-tubing work where the tubing size or completion components can impose a significant size restriction on devices designed to set in the casing or liner below the tubing.
  • Seal elements may either be bonded-type or chevron-type, and may employ seal elements comprising one or more elastomeric compositions described herein, and these elastomeric compositions may comprise one or more thermoplastic polymers, such as the polytetrafluoroethylene known under the trade designation TEFLON, available from E.I.
  • Formula A is a comparative example including no ionic bonding system of this invention.
  • Formulas B-C are compositions of this invention including 1.5 phr and 3.0 phr of an ionic bonding system of this invention.
  • the compositions are set forth in Table I based on 100 parts per hundred (phr) EPDM Rubber with equivalent general ingredients for compounds of rubber and Super Absorbent Polymer for aqueous swell. Test results for Formulas A-C are tabulated in Table II.
  • This example illustrates another preparation of an EPDM composition of this invention.
  • the composition is set forth in Table below based on 100 parts per hundred (phr) EPDM Rubber with equivalent amount of general ingredients for compounds of rubber and Super Absorbent Polymer for aqueous swell.
  • Table VII Ingredient List, Amounts and Properties FORMULA A H I MATERIAL phr phr phr Zinc Diacrylate 0 3 3 Aluminum Triacrylate 0 5 0 Calcium Diacrylate 0 0 5 Dicumyl Peroxide 40% effective 5 5 5 Table VIII Mass% Gain of a Compression Set Button: Fluid Ageing Specimens: Compression Set button having 0.49" thickness and 1.14" diameter Cured for 90 min.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP12187420.0A 2011-10-06 2012-10-05 Verbesserte quellbare Ölfeld-Elastomere und Herstellungs- und Verwendungsverfahren dafür Ceased EP2578622A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161544207P 2011-10-06 2011-10-06
US13/645,460 US9758658B2 (en) 2011-10-06 2012-10-04 Enhanced oilfield swellable elastomers and methods for making and using same

Publications (2)

Publication Number Publication Date
EP2578622A2 true EP2578622A2 (de) 2013-04-10
EP2578622A3 EP2578622A3 (de) 2013-05-29

Family

ID=47022501

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12187420.0A Ceased EP2578622A3 (de) 2011-10-06 2012-10-05 Verbesserte quellbare Ölfeld-Elastomere und Herstellungs- und Verwendungsverfahren dafür

Country Status (4)

Country Link
US (1) US9758658B2 (de)
EP (1) EP2578622A3 (de)
AU (1) AU2012238218B2 (de)
CA (1) CA2791468C (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104479198A (zh) * 2014-11-25 2015-04-01 苏州新区佳合塑胶有限公司 一种用于汽车上的塑料及其制备方法
US10125302B2 (en) 2014-09-29 2018-11-13 Halliburton Energy Services, Inc. Self-healing cement comprising polymer capable of swelling in gaseous environment
CN109021333A (zh) * 2018-06-18 2018-12-18 如皋千骏工具有限公司 一种海水泵橡胶叶轮的材料配方
CN110685616A (zh) * 2019-10-21 2020-01-14 江苏油田矿业开发有限公司 低渗水敏油井的修井作业方法
CN112625661A (zh) * 2021-03-05 2021-04-09 胜利油田固邦石油装备有限责任公司 一种降滤失剂及其制备方法

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8563481B2 (en) 2005-02-25 2013-10-22 Clearwater International Llc Corrosion inhibitor systems for low, moderate and high temperature fluids and methods for making and using same
US8871694B2 (en) 2005-12-09 2014-10-28 Sarkis R. Kakadjian Use of zeta potential modifiers to decrease the residual oil saturation
US8728989B2 (en) 2007-06-19 2014-05-20 Clearwater International Oil based concentrated slurries and methods for making and using same
US9945220B2 (en) 2008-10-08 2018-04-17 The Lubrizol Corporation Methods and system for creating high conductivity fractures
US9909404B2 (en) 2008-10-08 2018-03-06 The Lubrizol Corporation Method to consolidate solid materials during subterranean treatment operations
US8835364B2 (en) 2010-04-12 2014-09-16 Clearwater International, Llc Compositions and method for breaking hydraulic fracturing fluids
US8899328B2 (en) 2010-05-20 2014-12-02 Clearwater International Llc Resin sealant for zonal isolation and methods for making and using same
US8944164B2 (en) 2011-09-28 2015-02-03 Clearwater International Llc Aggregating reagents and methods for making and using same
US10604693B2 (en) 2012-09-25 2020-03-31 Weatherford Technology Holdings, Llc High water and brine swell elastomeric compositions and method for making and using same
US9429006B2 (en) 2013-03-01 2016-08-30 Baker Hughes Incorporated Method of enhancing fracture conductivity
US10669468B2 (en) 2013-10-08 2020-06-02 Weatherford Technology Holdings, Llc Reusable high performance water based drilling fluids
US9334337B2 (en) 2014-01-24 2016-05-10 Baker Hughes Incorporated Enhanced water swellable compositions
US10179873B1 (en) * 2014-03-06 2019-01-15 Weir Slurry Group, Inc. Water swellable rubber composition suitable for use with oil field equipment
US10202828B2 (en) 2014-04-21 2019-02-12 Weatherford Technology Holdings, Llc Self-degradable hydraulic diversion systems and methods for making and using same
DE102014008511B4 (de) 2014-06-03 2021-06-24 Gerhard Behrendt Verfahren zur Herstellung eines Formkörpers aus einem Füllstoffe enthaltenden Elastomer auf der Basis von Polyurethanen, nach dem Verfahren hergestellter Formkörper und Verwendung desselben
US10001769B2 (en) 2014-11-18 2018-06-19 Weatherford Technology Holdings, Llc Systems and methods for optimizing formation fracturing operations
US9976390B2 (en) * 2015-03-30 2018-05-22 Baker Hughes, A Ge Company, Llc Drilling fluids with leakoff control and drill cuttings removal sweeps
KR101833271B1 (ko) * 2015-04-01 2018-03-05 (주) 화승소재 자기 밀폐형 소재 및 그의 제조 방법
US9994746B2 (en) 2016-05-06 2018-06-12 Rl Hudson & Company Swellable packer seal composition
US11293247B2 (en) 2016-09-12 2022-04-05 Baker Hughes, A Ge Company, Llc Frac plug and method for fracturing a formation
US11492866B2 (en) * 2016-09-12 2022-11-08 Baker Hughes Holdings Llc Downhole tools containing ductile cementing materials
CN106928947B (zh) * 2017-03-28 2022-11-15 北京华油油气技术开发有限公司 一种套管间环空的封堵材料、封堵装置和封堵方法
WO2019121157A1 (de) * 2017-12-21 2019-06-27 Arlanxeo Deutschland Gmbh Hnbr-vulkanisat mit verbesserter heissluftbeständigkeit
CN108530902A (zh) * 2018-05-15 2018-09-14 许媛 一种基于丁氰橡胶改性的耐油硅橡胶及其制备方法
SG11202008674UA (en) 2018-06-28 2020-10-29 Halliburton Energy Services Inc Elastomer with an expandable metal
CN109400988B (zh) * 2018-11-08 2020-09-25 慈溪市春潮密封件有限公司 一种密封垫片及其制备方法
CN109777017B (zh) * 2019-01-30 2021-01-15 广东省石油与精细化工研究院 一种双网络磺化聚苯醚/丙烯酸脂类复合材料的制备方法
US10556829B1 (en) 2019-05-30 2020-02-11 Saudi Arabian Oil Company Cement slurries, cured cement and methods of making and use of these
GB2603335B (en) * 2019-10-23 2023-06-28 Halliburton Energy Services Inc Diclyclopentadiene as an oil swellable packer material
RU2767541C2 (ru) * 2020-04-03 2022-03-17 Акционерное общество "Федеральный научно-производственный центр "Прогресс" (АО "ФНПЦ "Прогресс") Нефтенабухающая резиновая смесь

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7373991B2 (en) 2005-07-18 2008-05-20 Schlumberger Technology Corporation Swellable elastomer-based apparatus, oilfield elements comprising same, and methods of using same in oilfield applications
US20090211770A1 (en) 2008-02-27 2009-08-27 Swelltec Limited Elongated Sealing Member for Downhole Tool
US20090211767A1 (en) 2008-02-27 2009-08-27 Swelltec Limited Expandable Member for Downhole Tool
US20090260801A1 (en) 2008-04-22 2009-10-22 Swelltec Limited Ring member for a swellable downhole packer
US20090272541A1 (en) 2006-11-21 2009-11-05 Swelltec Limited Downhole apparatus with a swellable connector
US20090277652A1 (en) 2008-03-04 2009-11-12 Swelltec Limited Swellable Packer Having a Cable Conduit

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5290844A (en) * 1989-07-28 1994-03-01 C. I. Kasei Co., Ltd. Water-swellable adhesive water stop
ATE240364T1 (de) * 1994-08-30 2003-05-15 Sartomer Co Inc Härtbare elastomere zusammensetzungen mit verbesserter entfernungseigenschaften
FR2779731B1 (fr) * 1998-06-11 2000-08-11 Hutchinson Composition d'elastomere a base d'epdm et courroie de transmission de puissance realisee essentiellement en cet elastomere
US7488705B2 (en) * 2004-12-08 2009-02-10 Halliburton Energy Services, Inc. Oilwell sealant compositions comprising alkali swellable latex
GB0711979D0 (en) * 2007-06-21 2007-08-01 Swelltec Ltd Method and apparatus
CN101698713B (zh) 2009-10-30 2011-08-03 武汉地铁集团有限公司 一种耐硫化氢腐蚀的遇水膨胀橡胶及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7373991B2 (en) 2005-07-18 2008-05-20 Schlumberger Technology Corporation Swellable elastomer-based apparatus, oilfield elements comprising same, and methods of using same in oilfield applications
US20090272541A1 (en) 2006-11-21 2009-11-05 Swelltec Limited Downhole apparatus with a swellable connector
US20090272525A1 (en) 2006-11-21 2009-11-05 Swelltec Limited Downhole apparatus with a swellable centraliser
US20090211770A1 (en) 2008-02-27 2009-08-27 Swelltec Limited Elongated Sealing Member for Downhole Tool
US20090211767A1 (en) 2008-02-27 2009-08-27 Swelltec Limited Expandable Member for Downhole Tool
US20090277652A1 (en) 2008-03-04 2009-11-12 Swelltec Limited Swellable Packer Having a Cable Conduit
US20090260801A1 (en) 2008-04-22 2009-10-22 Swelltec Limited Ring member for a swellable downhole packer

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10125302B2 (en) 2014-09-29 2018-11-13 Halliburton Energy Services, Inc. Self-healing cement comprising polymer capable of swelling in gaseous environment
CN104479198A (zh) * 2014-11-25 2015-04-01 苏州新区佳合塑胶有限公司 一种用于汽车上的塑料及其制备方法
CN109021333A (zh) * 2018-06-18 2018-12-18 如皋千骏工具有限公司 一种海水泵橡胶叶轮的材料配方
CN110685616A (zh) * 2019-10-21 2020-01-14 江苏油田矿业开发有限公司 低渗水敏油井的修井作业方法
CN112625661A (zh) * 2021-03-05 2021-04-09 胜利油田固邦石油装备有限责任公司 一种降滤失剂及其制备方法
CN112625661B (zh) * 2021-03-05 2021-06-22 胜利油田固邦石油装备有限责任公司 一种降滤失剂及其制备方法

Also Published As

Publication number Publication date
CA2791468C (en) 2016-05-10
CA2791468A1 (en) 2013-04-06
US9758658B2 (en) 2017-09-12
AU2012238218A1 (en) 2013-05-02
EP2578622A3 (de) 2013-05-29
AU2012238218B2 (en) 2014-05-22
US20130096038A1 (en) 2013-04-18

Similar Documents

Publication Publication Date Title
US9758658B2 (en) Enhanced oilfield swellable elastomers and methods for making and using same
US7373991B2 (en) Swellable elastomer-based apparatus, oilfield elements comprising same, and methods of using same in oilfield applications
US10604693B2 (en) High water and brine swell elastomeric compositions and method for making and using same
US9708523B2 (en) Swellable spacer fluids and associated methods
EP2981587B1 (de) Polymerzusammensetzungen für bohrlochanwendungen
CA2839522C (en) Composition of polybutadiene-based formula for downhole applications
EP1533469B1 (de) Dichtungsvorrichtung aus nanokompositem Material zur Verwendung im Bohrloch
US10336933B2 (en) Vulcanized oil and water swellable particulate composite compositions
EP2402551B1 (de) Fluorinierte Elastomerbohrlochschieberpacker und Verfahren
EP3068841B1 (de) Quellbare dichtungen und deren verwendung
CA3094342A1 (en) High performance fluoroelastomer bonded seal for downhole applications
US20160115367A1 (en) Ultrahigh Molecular Weight Polyethylene Reinforced Rubber Compositions For Subterranean Applications
RU2751316C1 (ru) Резиновая смесь
RU2759301C1 (ru) Способ снижения обводненности скважин и ликвидации внутрипластовых и межпластовых перетоков воды
US11851982B2 (en) Well tools with components formed from pyrolytically degradable materials
US20170183484A1 (en) Improved high temperature mechanical properties of elastomers with semi-crystalline polymers for downhole applications

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIC1 Information provided on ipc code assigned before grant

Ipc: C08L 23/16 20060101ALI20130425BHEP

Ipc: C08J 3/24 20060101AFI20130425BHEP

Ipc: C08K 5/14 20060101ALI20130425BHEP

Ipc: C08L 33/08 20060101ALI20130425BHEP

17P Request for examination filed

Effective date: 20131106

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

17Q First examination report despatched

Effective date: 20140114

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: WEATHERFORD/LAMB, INC.

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: WEATHERFORD TECHNOLOGY HOLDINGS, LLC

APBK Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNE

APBN Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2E

APBR Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3E

APAF Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNE

APBX Invitation to file observations in appeal sent

Free format text: ORIGINAL CODE: EPIDOSNOBA2E

APBT Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9E

111Z Information provided on other rights and legal means of execution

Free format text: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

Effective date: 20200511

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20200604

APBZ Receipt of observations in appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNOBA4E